- Sorption and degradation of azimsulfuron on iron(III)-rich soil colloids
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The sorption of N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl- 4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide (AZS) on an iron oxide, iron(III)-humate, and an Fe3+-saturated clay was studied using a batch equilibrium method. Generally, 20 mg of each colloid was equilibrated with 20 mL of AZS solution (1.5-12.7 μM). The sorption on iron-montmorillonite and iron oxide was rapid, and the equilibrium was attained within 1.5 and 5 h, respectively. In the case of Fe-saturated humic acid the equilibrium time was 20 h. After equilibration, the phases were centrifuged (19000g, 15 min) and the supernatant was sampled and analyzed by HPLC. The values of Freundlich constants indicate that iron oxide (Kads = 199-5) shows the highest sorptive capacity toward AZS, followed by iron(III)-clay (Kads = 146.6) and iron(III)-humate (Kads = 108.2). With elapsing time, AZS degradation was observed in all colloidal suspensions. Iron-humate (t1/2 = 136 h) is most effective in promoting AZS degradation, followed by iron oxide (t 1/2 = 204 h) and iron-clay (t1/2 = 385 h). The metabolites 2-amino-4,6-dimethoxypyrimidineand 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H- pyrazole-5-sulfonamide, arising from a hydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. A Fourier transform infrared study suggests that the sorption of AZS on iron-clay involves the protonation of one of the two basic pyrimidine nitrogens induced by the acidic water surrounding the saturating Fe3+ ions. Instead, the formation of a six-membered chelated complex favors the sorption of AZS on iron oxide.
- Pinna, M. Vittoria,Pusino, Alba,Gessa, Carlo
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- Synthesis of 2-amino-4,6-dimethoxypyrimidine with dimethyl carbonate as methylating agent
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2-amino-4,6-dimethoxypyrimidine (ADM) was prepared from 2-amino-4,6-dihydroxypyrimidine (ADH) in the presence of potassium carbonate and phase transfer catalyst (PTC), with dimethyl carbonate (DMC) instead of conventional toxic reagents (such as haloalkan
- Xiong, Zhen,Zhou, Minghao,Xiao, Guomin
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- Kinetic study on acid-base catalyzed hydrolysis of azimsulfuron, a sulfonylurea herbicide
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Pseudo-first-order rate constants (kobs) for hydrolysis of a sulfonylurea herbicide, azimsulfuron, AZIM, {N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbony]-1-methyl-4- (2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide} (AZS) follow an empirical relationship: kobs = α1+α2[-OH]+α3 [-OH]2 within the [NaOH] range of 0.1-2.0 M at different temperatures ranging from 40 to 55 °C. The contribution of α3[-OH]2 term is small compared with α2[-OH] term and this turns out to be zero at 60 °C. Pseudo-first-order rate constants (kobs) for hydrolysis of AZS within the [H+] range from 2.5×10-6 to 1.4 M follow the relationship: kobs = (α1Ka+β1[H*]+β2 [H+]2)/([H+]+Ka) where pKa = 4.37 at 50 °C. The value of β1 is nearly 25 times larger than that of α1. The rate of alkaline hydrolysis of AZIM is weakly sensitive to ionic strength.
- Khan, M. Niyaz,Bakar, Baki B.,Yin, Fenny W. N.
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- Chromatography and high-resolution mass spectrometry for the characterization of the degradation products of the photodegradation of amidosulfuron: An analytical approach
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Simulated sunlight irradiation causing degradation of amidosulfuron, a pyrimidinylsulfonylurea herbicide, has been investigated in aqueous solution. The main degradation products were followed up by ultrahigh-pressure liquid chromatography with a UV detector (UHPLC-UV) and identified by combining ultrahigh-pressure liquid chromatography-mass spectrometry (UHPLC-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). On the basis of the retrosynthetic analysis, the most identified degradation products were mainly due to the losses of methylsulfamic acid (CH5NO 3S), sulfocarbamic acid (CH3NO5S), carbamic acid (CH3NO2), methyl(methylsulfonyl)sulfamic acid (C 2H7NO5S2), N- methylmethanesulfonamide (C2H7NO2S), and sulfonic acid (H2SO4) molecules. Accordingly, O and S-demethylation as well as hydroxylation processes were also observed. Sum formulas of the main degradation products were assigned, and a mechanical pathway is proposed.
- Harir, Mourad,Chnirheb, Amina,Kanawati, Basem,El Azzouzi, Mohammed,Schmitt-Kopplin, Philippe
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- Preparation method of 2-amino-4, 6-dimethoxypyrimidine
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The invention discloses a preparation method of 2-amino-4, 6-dimethoxypyrimidine, which comprises the following steps: S1, reacting malononitrile with methanol and hydrogen chloride to prepare 1, 3-dimethoxymalonamidine dihydrochloride; S2, controlling the pH value to be 5-6, and adding cyanogen chloride to react with 1, 3-dimethoxypropane diamidine dihydrochloride, so as to prepare 3-amino-3-methoxy-N-nitrile-based 2-propylamidine; and S3, carrying out cyclization on the 3-amino-3-methoxy-N-nitrile-2-propylamidine to obtain 2-amino-4, 6-dimethoxy pyrimidine; wherein the reaction in the step S1-S3 is carried out in an organic solvent. The cyanide chloride is adopted to replace cyanamide in a traditional method, the water content of a synthesis system is reduced, the amount of three wastesis reduced, a target product is synthesized through a one-pot method, damage caused by high corrosivity of 1, 3-dimethoxypropane diamidine dihydrochloride is avoided, the synthesis time is shortened,and the production efficiency is improved.
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Paragraph 0028; 0031; 0032; 0035; 0036; 0039
(2021/03/30)
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- Preparation method of 2-amino-4,6-dimethoxypyrimidine
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A preparation method of 2-amino-4,6-diamino-1,3,4-triazole comprises the following steps: malononitrile and methanol which are used as raw materials undergo a hydrogen chloride aeration reaction in asolvent which is one of methylbenzene, dimethylbenzene, chlorobenzene and dichloroethane to generate 1,3-dimethoxypropylenediamine dihydrochloride, a water-insoluble quaternary amine organic alkali isdropwise added into the obtained reaction system without filtration or other post-treatment operations in order to regulate the pH value of the reaction system to 6-8, a cyanamide solid is added, a reaction is performed to generate 3-amino-3-methoxy-N-nitrile-2-propylamidine, and the 3-amino-3-methoxy-N-nitrile-2-propylamidine is heated to react to generate the 2-amino-4,6-dimethoxypyrimidine product. The method for preparing the 2-amino-4,6-dimethoxypyrimidine by using a one-pot process has the advantages of mild reaction conditions, safety, environmental friendliness, process operation simplification, and small amount of three wastes, makes the total synthesis yield of the four-step reaction reach 80% or above and the product content reach 99% or above, and is suitable for green industrial production.
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Paragraph 0030; 0032; 0035; 0037; 0040; 0042; 0045; 0047
(2020/04/02)
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- Preparation method for 2-amino-4,6-dimethoxypyrimidine
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The invention provides a preparation method for 2-amino-4,6-dimethoxypyrimidine. The method comprises the following steps: by using malonate diester (II) and a di-substituted methylene guanidine salt(III) as raw materials, performing a cyclization reaction under the action of a base, performing a methylation reaction with a methylation reagent to prepare 2-di-substituted methylene amino-4,6-dimethoxypyrimidine (IV), and performing hydrolysis in an acidic aqueous solution to prepare the 2-amino-4,6-dimethoxypyrimidine (I). The raw materials used in the method are cheap and easy to obtain, andthe costs are low; the preparation method is simple, the steps are few, the conditions are easy to realize, and the operational safety is good; and the product yield and purity are high, the amount ofwastewater is small, and the method is environmentally friendly and suitable for industrial production.
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Paragraph 0050-0053; 0056-0059
(2020/03/05)
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- Microwave-assisted synthesis and docking studies of phenylureas as candidates for the drug design against the biological warfare agent Yersinia pestis
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Background: Bubonic plague is amongst the diseases with the highest potential for being used in biological warfare attacks today. Introduction: This disease, caused by the bacterium Yersina pestis, is highly infectious and can achieve 100% of fatal victims when in its most dangerous form. Besides, there is no effective vac-cine, and the chemotherapy available today against plague is ineffective if not administered at the beginning of the infection. Willing to contribute for changing this reality we propose here new phe-nylureas as candidates for the drug design against plague meant to target the enzyme dihydrofolate reductase from Y. pestis (YpDHFR). Methods: Seven phenylureas, four of them new, were synthesized, following synthetic routes adapted from procedures available in the literature, and using microwave irradiation. After, they were submitted to docking studies inside YpDHFR and human DHFR (HssDHFR) in order to check their potential as selective inhibitors. Results & Conclusion: Our results revealed four new phenylureas and a new synthetic route for this kind of molecule using microwave irradiation. Also, our docking studies pointed to two of the phe-nylureas as selective inhibitors of YpDHFR and, therefore, candidates for the design of new drugs against plague.
- Bastos, Leonardo da Costa,Bendahan, David,Chacón-Huete, Franklin,Cuya, Teobaldo,Forgione, Pat,Fran?a, Tanos Celmar Costa,Sirouspour, Mehdi
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p. 631 - 637
(2020/04/17)
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- Method for preparing 2-amino-4,6-dimethoxy pyrimidine
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The invention relates to a method for preparing 2-amino-4,6-dimethoxy pyrimidine. The method comprises the following steps: by taking 3-amino-3-methoxy-N-cyano-2-pyridinepropanimidamide as a raw material, and carrying out cyclization under the action of a catalyst, so as to generate the 2-amino-4,6-dimethoxy pyrimidine. By adopting the method, not only is a production cycle shortened, but also thereaction temperature is reduced, in addition, the product purity is improved, an economic and energy-saving route is provided for industrial production of the 2-amino-4,6-dimethoxy pyrimidine, and good economic benefits can be made. The structural formula of the 2-amino-4,6-dimethoxy pyrimidine is shown in the specification.
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Paragraph 0024-0052
(2019/10/01)
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- Integrated synthetic method of 2-amino-4,6-dimethoxypyrimidine
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The invention provides an integrated synthetic method of 2-amino-4,6-dimethoxypyrimidine, belongs to the technical field of organic synthesis, and provides a synthetic route using malononitrile, methanol, acetyl chloride, cyanamide and alkali liquid as raw materials. The integrated synthetic method comprises the following steps: dropwise adding acetyl chloride into a system of malononitrile and methanol to directly obtain 1,3-dimethyl propadiamidine dihydrochloride, and then performing reaction on 1,3-dimethyl propadiamidine dihydrochloride and the alkali liquid and cyanamide to obtain 3-amino-3-methoxyl-N-nitril-2-propa-amidine; directly heating, evaporating solvent and performing distillation to obtain 2-amino-4,6-dimethoxypyrimidine. According to the synthetic method disclosed by the invention, a synthetic process and equipment of 1,3-dimethyl propadiamidine dihydrochloride are simple, moisture control of the system is extremely low, the quality of the product is stable, and the yield is high. By adopting the integrated synthetic process, the synthetic process is reduced, distillation is carried out under reduced pressure so as to obtain 2-amino-4,6-dimethoxypyrimidine, and thepurity of the product is up to 99.99 percent.
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Paragraph 0022; 0023; 0028; 0029; 0030-0032; 0037-0039
(2018/03/28)
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- 2-amino-4,6-dimethoxypyrimidine synthesis method
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The invention provides a 2-amino-4,6-dimethoxypyrimidine synthesis method, which belongs to the technical field of organic synthesis. The invention provides a synthetic route which takes malononitrile, methanol, acetyl chloride, hydrogen cyanamide and alkali liquor as raw materials; the method comprises the following steps of dropwise adding the acetyl chloride to a system of the malononitrile andthe methanol, directly obtaining 1,3-dimethylpropanediamidine dihydrochloride, then reacting with the alkali liquor and the hydrogen cyanamide to obtain 3-amino-3-methoxy-N-cyano-2-propylamidine andfurther performing closed-loop rearrangement to obtain 2-amino-4,6-dimethoxypyrimidine. The synthesis method provided by the invention saves the cumbersome synthesis technology and equipment of the 1,3-dimethylpropanediamidine dihydrochloride, and comprises the steps of adding the acetyl chloride into the malononitrile and the methanol to directly obtain the 1,3-dimethylpropanediamidine dihydrochloride. The synthetic route of the 1,3-dimethylpropanediamidine dihydrochloride in the invention has extremely low moisture control, stable product quality and high yield.
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Paragraph 0022; 0028; 0029; 0038
(2018/03/28)
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- Investigation of novel pesticides with insecticidal and antifungal activities: Design, synthesis and SAR studies of benzoylpyrimidinylurea derivatives
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In order to find pesticides with insecticidal and antifungal activities, a series of novel benzoyl pyrimidinylurea derivatives were designed and synthesized. All target compounds were identified by 1H-NMR spectroscopy and HRMS. Insecticidal and antifungal activity of these compounds were evaluated and the structure-activity relationships (SAR) were clearly and comprehensively illustrated. Compound 7, with low toxicity to zebrafish (LC50 = 378.387 μg mL?1) showed 100% inhibition against mosquito (Culex pipiens pallens) at 0.25 μg mL?1. Both compounds 19 and 25 exhibited broad-spectrum fungicidal activity (>50% inhibitory activities against 13 phytopathogenic fungi), which were better than those of the commercial pesticide pyrimethanil (>50% inhibitory activities against eight phytopathogenic fungi). Furthermore, compounds 19 and 25 exhibited protective activity against Sclerotinia sclerotiorum on leaves of Brassica oleracea L. during in vivo experiments.
- Chen, Peiqi,Song, Xiangmin,Fan, Yongmei,Kong, Weihao,Zhang, Hao,Sun, Ranfeng
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- A novel benzoyl pyrimidine urea compound and its preparation and use (by machine translation)
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The invention provides a benzoyl pyrimidine urea compound, of formula I or formula II structure shown. The present invention provides benzoyl pyrimidine urea compound has excellent armyworm killing, mosquito killing and broad-spectrum antifungal activity. The experimental result shows, the present invention provides benzoyl pyrimidine urea compound in 0.5 μg mL- 1 Sliding surface of larvae activity can be up to 100%, in the 0.25μg mL- 1 Sliding surface of larvae activity can be up to 100%. In the 50 μg mL- 1 When, demonstrated broad-spectrum antifungal activity, and to the cabbage in vitro blade has a certain protective effect. And low toxicity to fish, LC to the zebra fish50 Are respectively 378.387 mg L- 1 , 21.668 Mg L- 1 . Can be used to prepare insecticidal, anti-plant-pathogenic fungi pesticide application. (by machine translation)
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Paragraph 0058; 0059; 0060; 0062; 0064
(2019/01/06)
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- A 2 - amino - 4, 6 - dimethoxy pyrimidine preparation method
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The invention relates to the technical field of synthesis of an important midbody of medicine and chemicals, and particularly relates to a preparation method of 2-amino-4, 6-dimethoxy pyrimidine. According to the method, malononitrile is used as a basic raw material, a target object is prepared by virtue of reaction such as imidization, cyanamide substitution, aromatization cyclization and the like, particularly an aromatization cyclization optimization process is innovatively designed, so that the preparation method has characteristics of high yield, high purity and low cost. The improved process is simple in procedures, easy to industrialize, smooth to operate, less in waste gas, waste water and waste residue and environment-friendly, has remarkable social benefit and economic benefit and is suitable for industrialized production.
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Paragraph 0035; 0036; 0037; 0038; 0039; 0046; 0047-0049
(2017/12/04)
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- HAIR COLOURANTS COMPRISING TETRAAMINOPYRIMIDINE DERIVATES
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The present disclosure relates to compositions for colouring keratin fibres, in particular human hair, where the composition comprises, in a cosmetic carrier, at least one neutral tetraaminopyrimidine derivate of the general formula (I), (I) in which R1, R2 independently of one another are a group of the formulae (II), (III) or (IV) —(CH2)n— (II) —(CH2)m—O—(CH2)p— (III) —(CH2)m—N(R3)-(CH2)p— (IV) n is 2, 3, 4, 5 or 6, m, p in each case independently of one another are 1, 2 or 3, Y is —OH, —NH2 or —NH-alkyl, R3 is a hydrogen atom, a C1-C6-alkyl group or is a C2-C6-alkenyl group.
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Paragraph 0213; 0214; 0215; 0216
(2017/11/29)
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- 2 - amino - 4, 6 - dimethoxy pyrimidine and its preparation method
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The invention provides 2-amino-4,6-dimethoxypyrimidine and a preparation method thereof. The method comprises the following steps: S1, mixing an organic solution containing malononitrile, a first solvent and a first catalyst, introducing hydrogen chloride into the mixed liquor, and stirring for reacting to obtain a hydrochloride solution of dimethoxypropyldiamidine; S2, adding hydrogen cyanamide into a buffer solution, stirring the solution, adding the hydrochloride solution of the dimethoxypropyldiamidine, and separating an obtained reaction solution to obtain cyanopropdimethyl diimide; and S3, dissolving the cyanopropdimethyl diimide into a second solvent, adding a second catalyst into a solvent suspension, and treating a reaction product to obtain the 2-amino-4,6-dimethoxypyrimidine. The hydrochloride solution of the dimethoxypropyldiamidine serving as an intermediate is directly added into the buffer solution containing the hydrogen cyanamide for reacting without being separated, and the reaction product is separated, so that the yield and purity of a final product are increased.
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Paragraph 0023; 0043-0046
(2017/06/13)
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- MEANS FOR OXIDATIVE DYEING OF KERATIN FIBERS CONTAINING NOVEL TETRA-SUBSTITUTED DERIVATIVES OF PYRIMIDINE
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Agents for oxidatively dyeing keratinous fibers include, in a cosmetic carrier, as an oxidation dye precursor of the developer type, at least one compound of formula (I) as set forth herein, in which R1, R2 can stand independently of each other, for a hydrogen atom, different substituted alkyl groups, and/or different substituted acrylic groups, and Y stands for a hydroxyl group, an amino group, or a C1-C6 alkylamino group, with the proviso that at least one of the moieties from the group R1 and R2 does not stand for a hydrogen atom, and/or the physiologically compatible salt thereof.
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Paragraph 0258-0262
(2016/10/31)
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- Method for preparing 2-amino-4,6-dimethoxy pyrimidine
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The invention relates to the field of chemical industry, particularly a method for preparing 2-amino-4,6-dimethoxy pyrimidine. The method comprises the following steps: by using 1,3-dimethoxypropyldiimine dihydrochloride as a raw material, adding an alkali and xanthogenamide into a reaction solvent to react, thereby obtaining a material 1; and heating the material 1 to perform cyclization and degassing, thereby obtaining the synthetic target product 2-amino-4,6-dimethoxy pyrimidine.
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Paragraph 0040; 0041
(2016/10/31)
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- Synthesis of 2-amino -4,6-dimethoxypyrimidine production method
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The invention relates to a production method of synthesizing 2-amino-4,6-dimethoxy pyrimidine. The production method comprises the following steps: with 2-chloro-4,6-dimethoxy pyrimidine as a raw material, carrying out a pressurization ammonolysis reaction on the raw material and ammonia gas in a high-pressure autoclave, directly cooling the reacted mixture to separate out crystals, carrying out solid-liquid separation on the mixture, and drying the solid to obtain 2-amino-4,6-dimethoxy pyrimidine, wherein the separated liquid can be directly recycled. The production method disclosed by the invention is a green production method; the pyrimidine produced by using the production process is high in amine yield, low in production cost, high in purify, simple to operate, environment-friendly and suitable for industrial production.
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Paragraph 0049; 0050
(2016/10/08)
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- Orally Bioavailable Metal Chelators and Radical Scavengers: Multifunctional Antioxidants for the Coadjutant Treatment of Neurodegenerative Diseases
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Neurodegenerative diseases are associated with oxidative stress that is induced by the presence of reactive oxygen species and the abnormal cellular accumulation of transition metals. Here, a new series of orally bioavailable multifunctional antioxidants (MFAO-2s) possessing a 2-diacetylamino-5-hydroxypyrimidine moiety is described. These MFAO-2s demonstrate both free radical and metal attenuating properties that are similar to the original published MFAO-1s that are based on 1-N,N′-dimethylsulfamoyl-1-4-(2-pyrimidyl)piperazine. Oral bioavailability studies in C57BL/6 mice demonstrate that the MFAO-2s accumulate in the brain at significantly higher levels than the MFAO-1s while achieving similar neural retina levels. The MFAO-2s protect human neuroblastoma and retinal pigmented epithelial cells against hydroxyl radicals in a dose-dependent manner by maintaining cell viability and intracellular glutathione levels. The MFAO-2s outperform clioquinol, a metal attenuator that has been investigated for the treatment of Alzheimer's disease.
- Kawada, Hiroyoshi,Kador, Peter F.
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p. 8796 - 8805
(2015/12/09)
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- NEUROPROTECTIVE MULTIFUNCTIONAL ANTIOXIDANTS AND THEIR MONOFUNCTIONAL ANALOGS
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The neuroprotective multifunctional antioxidants are compounds that contain a 2-diacetylamino-5-hydroxypyrimidine moiety, having the structural formula: wherein R1 is CH2 or C2H4; R2 is H or —OR4 where R4 is H or aryl; and R3a and R3b are independently selected from the group consisting of H and —O-alkyl. The antioxidants are orally bioavailable metal-attenuating multifunctional antioxidants that can independently attenuate transition metals, as well as scavenger free radicals. The multifunctional antioxidant compounds, by their ability to independently chelate metals, such as Fe, Cu or Zn, and scavenge free radicals generated from different sources, are neuroprotective and are beneficial for the treatment of various neurological disorders, such as Alzheimer's disease, Parkinson's disease, ALS, traumatic brain injury, ocular disorders, such as cataract, glaucoma, age-related macular degeneration and other retinal degeneration, as well as for reducing the progression of diabetic complications.
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Paragraph 0059
(2014/09/03)
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
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A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
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supporting information
p. 3734 - 3737
(2013/08/23)
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- Structural elucidation of phototransformation products of azimsulfuron in water
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The photodegradation of the sulfonylurea herbicide azimsulfuron, N-[[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-1-methyl-4-(2-methyl-2H- tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS), was studied in water at different wavelengths and in the presence of photocatalysts. AZS was rapidly degraded by UV light, affording three photoproducts. The main product, accounting for about 70% of photodegraded herbicide, was identified as 6-amino-5-[(4,6-dimethoxypyrimidin-2-yl)methylamino]-1,5,6,8-tetrahydro-7-oxa- 8A6-tia-1,2,5,6-tetraza-azulen-4-one (ADTA) by single-crystal X-ray diffraction. With simulated sunlight irradiation, the reaction was slower and 2-amino-4,6-dimethoxypyrimidine (DPA) and 1-methyl-4-(2-methyl-2H-tetrazole-5- yl)-1H-pyrazole-5-sulfonamide (MPS), arising from a photohydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. The reactions followed first-order kinetics. The addition of dissolved organic matter (DOM) did not modify significantly the AZS photodegradation rate. The presence of Fe2O3 accelerated more than twice the reaction rate affording two major products, DPA and MPS, together with minor amounts of N-[[(5-hydroxy-4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl- 2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS-OH). The greatest degradation rate was detected in the presence of TiO2. Only the photohydroxylation product AZS-OH was observed, which was transformed rapidly into oxalic acid.
- Pinna, M. Victoria,Zema, Michele,Gessa, Carlo,Pusino, Alba
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p. 6659 - 6663
(2008/09/17)
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- Pharmaceutically active pyrrolidine derivatives
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The present invention is related to pyrrolidine derivatives of formula (I). Said compounds are preferably for use as pharmaceutically active compounds. Specifically, pyrrolidine derivatives of formula (I) are useful in the treatment and/or prevention of premature labor, premature birth and dysmenorrhea. In particular, the present invention is related to pyrrolidine derivatives displaying a substantial modulatory, notably an antagonist activity of the oxytocin receptor. More preferably, said compounds are useful in the treatment and/or prevention of disease states mediated by oxytocin, including premature labor, premature birth and dysmenorrhea. The present invention is furthermore related to novel pyrrolidine derivatives as well as to methods of their preparation, wherein X is selected from the group consisting of CR6R7, NOR6, NNR6R7; A is selected from the group consisting of —(C═O)—, —(C═O)—O—, —C(═NH)—, —(C═O)—NH—, —(C═S)—NH, —SO22—, —SO2NH—, —CH2—,B is either a group —(C═O)—NR8R9 or represents a heterocyclic residue having the formula (a) wherein Q is NR10, O or S; n is an integer selected of 0, 1 or 2; Y, Z and E form together with the 2 carbons to which they are attached a 5-6 membered aryl or heteroaryl ring.
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- Pharmaceutically active pyrrolidine derivatives as bax inhibitors
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The present invention is related to new substituted pyrrolidine derivatives of formula (I). Said compounds are preferably for use as pharmaceutically active compounds. Specifically, pyrrolidine derivatives of formula (I) are useful in the treatment and/or prevention of neurodegenerative disorders, diseases associated with polygultamine tracts, epilepsy, ischemia, infertility, cardiovascular disorders renal hypoxia, hepatitis and AIDS. Said pyrrolidine derivatives display a modulatory and most notably a down-regulating-up to an inhibitory-activity with respect to the cellular death agonist Bax and/or the activation pathways leading to Bax and allows therefore to block the release of cytochrome (c). The present invention is furthermore related to novel pharmaceutically activity substituted pyrrolidine derivatives as well as to methods of their preparation, wherein X is selected from the group consisting of O, S, CRR, NOR, NNRR; A is selected from the group consisting of —(C═O)—, —(C═O)—O—, —C(═NH)—, —(C═O)—NH—, —(C═S)—NH, —SO2-, —SO2NH—; —CH2-; B is either a group —(C═O)—NRR or represents a heterocyclic residue having the formula (II) wherein Q is NR, O or S; n is an integer selected of 0, 1 or 2; Y, Z and E form together with the 2 carbons to which they are attached a 5-6 membered aryl or heteroaryl ring.
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- Nicosulfuron: Alcoholysis, chemical hydrolysis, and degradation on various minerals
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Alcoholysis (methanol or ethanol) and hydrolysis (pH ranging from 4 to 11) of the herbicide nicosulfuron at 30 °C principally involves the breakdown of the urea part of the molecule. A high yield of the corresponding carbarnate was obtained along with aminopyrimidine during alcoholysis. Hydrolysis led to both aminopyrimidine and pyridylsulfonamide. The latter compound may be easily cyclized (pH ≥ 7). First-order kinetics describe the rates of alcoholysis and hydrolysis well. The rate constants (0.44 days-1 for methanolysis) decreased from 0.50 to 0.002 days-1 as pH increased from 4 to 8, then remained stable under alkaline conditions. In acidic or neutral solution, the hydrolysis path appeared prevalent (≥70%), whereas in an alkaline medium it decreased when pH increased. The chemical degradation of nicosulfuron on various dry minerals (calcium bentonite, kaolinite, silica gel, H+ bentonite, montmorillonite K10, and alumina) was investigated at 30 °C. The best conditions for the degradation are obtained on acidic minerals after herbicide deposition using the liquid method. Under these conditions an acceptable correlation with pseudo-first-order kinetics was observed, and the major degradation path is similar to that proposed for chemical hydrolysis. Conversely, alumina seemed to favor other unknown degradation processes. The hydrolysis paths of nicosulfuron and rimsulfuron appeared to be different.
- Sabadie, Jean
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p. 526 - 531
(2007/10/03)
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- Fate and behaviour of flupyrsulfuron-methyl in soil and aquatic systems
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The environmental fate of [14C] flupyrsulfuron-methyl, a sulfonylurea herbicide, was investigated in soil and aquatic systems. The major degradative pathways in both systems were contraction of the sulfonylurea bridge followed by intramolecular rearrangement (at pH > 7) or sulfonylurea bridge hydrolysis (at pH 50 3-6 days), degradation being faster in the aerobic aquatic systems than in sterile buffers. Degradation in aerobic soils was rapid, both in the laboratory (DT50 8-26 days) and in the field (DT50 6- 11 days, DT90 35-123 days). In laboratory studies the rate of degradation in soil reduced with decreasing temperature (rate at 10°C half that at 20°C) but was unaffected by soil water content (50% vs 70% maximum water holding capacity). The compound was degraded in flooded anaerobic soils (DT50 33 days). Flupyrsulfuron-methyl was weakly absorbed to soils, there being a linear relationship between adsorption and soil organic carbon content. Following application of [14C]flupyrsulfuron-methyl to bare field soil the radioactivity moved little, with very little radioactivity found in soil below 60 cm from the surface.
- Singles,Dean,Kirkpatrick,Mayo,Langford-Pollard,Barefoot,Bramble F.Q.
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p. 288 - 300
(2007/10/03)
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- Intramolecular and bimolecular nucleophilic substitutions of rimsulfuron sulfonylurea
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The sulfonylurea herbicide rimsulfuron 1 (N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-(ethylsulfonyl)-2-pyridinesulfonamide) in aqueous solutions of KOH, NaOH, NH4OH, or dilute HCl, and thermally (rimsulfuron or monomethylated rimsulfuron at the sulfonamide hydrogen) was transformed by SO2 extrusion and intramolecular nucleophilic substitution into 2-(N-(4,6-dimethoxy)pyrimidin-2-yl)amino-3-ethylsulfonylpyridine 3.In mild methanol + HCl conditions, the intermediate rearranged urea N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinyl)urea 2 was isolated.In concentrated hydrochloric acid, rimsulfuron 1 was transformed by bimolecular nucleophilic substitution successively into 2-chloro-3-ethylsulfonylpyridine 6 and 2-hydroxy-3-ethylsulfonylpyridine 4.Sodium sulfite transformed rimsulfuron 1 into a mixture of 2-sodiumsulfonate-3-ethylsulfonylpyridine 7 and amine 3.
- Rouchaud, J.,Neus, O.,Moulard, C.
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- Soil Metabolism of the Herbicide Laboratory and Field Conditions
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Procedures were developed for soil analysis of rimsulfuron and its metabolites by means of GC-ECD, GC-FPD and GC-MS with a detection limit of 1 μg of rimsulfuron equivalents per kilogram of dry soil, after purification of the soil extracts by TLC. Soil containing an exaggerated rimsulfuron concentration was incubated in the laboratory, in order to adjust the analytical procedures. To evaluate the role of different manuring managements, rimsulfuron was applied postemergence (10 g ha-1 on a corn field in 1994 and 1995) on plots treated with (1) green manure, pig slurry applied in (2) November and (3) March, and cow manure applied in (4) November and (5) March and (6) untreated control plots without organic fertilizer. Neither rimsulfuron nor its metabolites were detected at soil depths lower than 8 cm. The results show that manure managements prolong rimsulfuron half-life in the 0-8 cm surface soil layer from a minimum of 14 days (control) to a maximum of 46 days (pig slurry in March). At corn harvest, rimsulfuron and its metabolites were not detected in soil. Similar soil degradation pathways were observed in the field as in the laboratory. N-(4,6-Dimethoxypyrimidin-2-yl)-N-[3-(ethylsulfonyl)-2-pyridinyl]urea 2 was a transient soil degradation product. N-[3-(ethylsulfonyl)-2-pyridinyl]-4,6-dimethoxy-2-pyrimidineamme 3 attained a maximum soil concentration after 20 days of incubation and then progressively disappeared and could not be detected after 40 days. The high-molecular weight amine 3 did not accumulate in soil, eliminating the concern for potential formation of nitroso amino compounds. 2-Hydroxy-3-(ethylsulfonyl)pyridine 4 became the major rimsulfuron soil degradation product. The soil concentrations increased and attained a maximum after 40 days of incubation and then decreased; its isomerization into 2-pyridone, followed by hydrolysis, could transform it into low molecular weight nontoxic products. The concentrations of 2-amino-4,6-dimethoxypyrimidine 5 were somewhat lower than those of compound 4.
- Rouchaud, Jean,Neus, Olivier,Callens, Dany,Bulcke, Robert
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p. 3283 - 3291
(2007/10/03)
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- Dimethoxypyrimidines as Novel Herbicides. Part 1. Synthesis and Herbicidal Activity of Dimethoxyphenoxypyrimidines and Analogues
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A number of 6-(4-phenoxyphenoxy)pyrimidines and triazines were synthesized and their herbicidal activity was measured. Compounds with the methoxy groups at the 2- and 4-positions on the pyrimidine and triazine rings exhibited high herbicidal activity. Introduction of a substituent into the 5-position of the pyrimidine ring diminished the activity. In the phenoxyphenoxy substructure at the 6-position, the central ether bond can be replaced by a methylene group without loss of activity. The optimum substituent on the terminal phenyl ring was 3-trifluoromethyl. The compounds showed a strong Hill reaction inhibition, but unfortunately showed poor selectivity between weeds and crops. - Keywords: phenoxyphenoxypyrimidines; phenoxyphenoxy-s-triazines; Hill reaction inhibitors; 2,6-dimethoxy-4-pyrimidine; 2,6-dimethoxy-4--s-triazine; herbicides
- Nezu, Yukio,Miyazaki, Masahiro,Sugiyama, Kazuhiko,Kajiwara, Ikuo
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p. 103 - 114
(2007/10/03)
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- Process for the preparation of aminopyrimidines
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2-Aminopyrimidines of the formula I STR1 in which X and Y are O or S and R1 and R2 independently of one another are lower alkyl, alkoxyalkyl or haloalkyl, are obtained by reacting propanediimidates of the formula II or salts thereof with cyanamide in the presence of a base at pH values above pH 7. The process allows the aminopyrimidines to be prepared in a one-pot reaction
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- Process for the preparation of aminopyrimidines
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Aminopyrimidines of the formula (I) STR1 in which X and Y are in each case oxygen or sulfur and R1, R2 are independently of one another (C1 -C4)alkyl, (C1 -C4)alkoxy-(C1 -C2)alkyl or halo(C1 -C4)alkyl, are intermediates for the preparation of herbicides from the sulfonylurea group. According to the invention, compounds of the formula I can be prepared in a one-step process without pH control, which comprises the reaction of a propanediimidate of the formula or its salt with an alkali metal or alkaline earth metal salt of the cyanamide, in which a solution of the compounds in an alcohol of the formula R4 --OH, in which R4 is (C1 -C6)alkyl, or, simultaneously, separate solutions of the compounds in each case in an alcohol R4 --OH are added to an inert organic solvent which is higher-boiling in comparison to the alcohol at temperatures above 100° C. with simultaneous removal of the alcohol by distillation.
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- Process for the preparation of pyrimidines
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The invention relates to a process for the preparation of compounds of the formula I STR1 in which X and Y denote O or S; R1 and R2 denote (substituted) alkyl, R3 denotes H or a --COR4 radical in which R4 is alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, (substituted) phenyl or (substituted) phenoxy, wherein a propanediimidate of the formula II STR2 or a salt thereof is reacted, in an inert solvent and in the presence of a base, with a carbonic acid imine derivative of the formula III STR3 in which R5 denotes halogen, alkoxy, alkylthio, phenoxy or phenylthio.
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- Process for producing sulfonylureas
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There is described a novel process for producing sulfonylureas of formula I STR1 wherein R1 is hydrogen or alkyl, R2 is STR2 E is =N-- or =CH--, R3 is alkyl, alkoxy or halogen, R4 is alkyl, cycloalkyl, alkoxy, halogen, alkoxy-alkyl, halo-alkyl or halo-alkoxy, R5 is hydrogen or alkyl, T is a substituted phenyl group STR3 Y is hydrogen or halogen, X is hydrogen, halogen, alkyl, halo-alkyl, alkenyl, halo-alkenyl, alkynyl, alkoxy, halo-alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halo-alkylthio, alkylsulfonyloxy, phenylsulfonyloxy, phenylsulfonyloxy mono- or polysubstituted by alkyl, or is di-alkylsulfamoyl, and A is a bridge member which has 3 or 4 atoms and which contains 1 or 2 hetero atoms, selected from the group consisting of oxygen, sulfur and nitrogen, the said process comprising reacting a silfonamide of the formula II in the presence of a base, with diphenyl carbonate to form a salt of a phenyl carbamate converting this salt into the free phenyl carbamate and reacting this further with an amine. Sulfonylureas are herbicidally effective compounds.
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- Propenimidates
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Propenimidates are provided having the formula: STR1 wherein X and Y are independently O or S; and R1 and R2 are independently C1 -C4 alkyl, (CH2)n OR3 where R3 is C1 -C4 alkyl and n is 1 or 2, CH2 CH2 Cl, or CH2 CF3, provided that when R1 or R2 is CH2 CH2 Cl or CH2 CF3, then the respective X or Y is O. Preferred propenimidates have X and Y as O and R1 and R2 as methyl or ethyl. The propenimidates are made by preparing a monohydrohalide salt from a dihydrohalide salt of the formula: STR2 and then contacting the monohydrohalide salt with cyanamide. The propenimidates upon heating ring close to pyrimidines which are useful in preparing herbicidal compounds.
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